RhI-Catalyzed Stille-Type Coupling of Diazoesters with Aryl Trimethylstannanes

2015 ◽  
Vol 68 (9) ◽  
pp. 1379 ◽  
Author(s):  
Zhen Liu ◽  
Ying Xia ◽  
Sheng Feng ◽  
Shuai Wang ◽  
Di Qiu ◽  
...  
Keyword(s):  
Diazo Compound ◽  
Cross Coupling ◽  
Mild Conditions ◽  
Alternative Approach ◽  
Migratory Insertion ◽  
Type Coupling ◽  
Insertion Process ◽  
Coupling Partner

A RhI-catalyzed cross-coupling of diazoester with arylstannane was developed. This reaction represents the first Stille-type coupling that uses a diazo compound as the coupling partner. The reaction is operationally simple and can be carried out under mild conditions, thus providing an alternative approach for the synthesis of α-aryl esters. RhI–carbene migratory insertion process is suggested to be involved as the key step in this Stille-type coupling.

Pd-catalyzed cross-coupling of terminal alkynes with ene-yne-ketones: access to conjugated enynes via metal carbene migratory insertion

2015 ◽  
Vol 51 (56) ◽  
pp. 11233-11235 ◽  
Author(s):  
Ying Xia ◽  
Zhen Liu ◽  
Rui Ge ◽  
Qing Xiao ◽  
Yan Zhang ◽  
...  
Keyword(s):  
Bond Formation ◽  
Cross Coupling ◽  
Terminal Alkynes ◽  
Conjugated Enynes ◽  
Migratory Insertion ◽  
Insertion Process

Pd-catalyzed oxidative cross-coupling of terminal alkynes with ene-yne-ketones has been developed, in which the ene-yne-ketones are served as carbene precursors and metal carbene migratory insertion process is the key step for C–C bond formation.

scholarly journals Non-Symmetrical Bis-Azine Biaryls from Chloroazines: A Strategy Using Phosphorus Ligand-Coupling

2019 ◽  
Author(s):  
Benjamin T. Boyle ◽  
Michael C. Hilton ◽  
Andrew McNally
Keyword(s):  
Cross Coupling ◽  
Coupling Reactions ◽  
One Pot ◽  
Cross Coupling Reactions ◽  
Alternative Approach ◽  
Metal Catalyzed ◽  
Traditional Approaches ◽  
Coupling Partner ◽  
Coupling Sequence

Distinct approaches to synthesize bis-azine biaryls are in demand as these compounds have multiple applications in the chemical sciences and are challenging targets for metal-catalyzed cross-coupling reactions. Most approaches focus on developing new reagents as the formal nucleophilic coupling partner that can function in metal-catalyzed processes. We present an alternative approach using pyridine and diazine phosphines as nucleophilic partners and chloroazines where the heterobiaryl bond is formed via a tandem S<sub><i>N</i></sub>Ar-phosphorus ligand-coupling sequence. The heteroaryl phosphines are prepared from chloroazines and are bench stable solids. Using this strategy, a range of bis-azine biaryls can be formed from abundant chloroazines that would be challenging using traditional approaches and a one-pot cross-electrophile coupling of two chloroazines is feasible.

scholarly journals Non-Symmetrical Bis-Azine Biaryls from Chloroazines: A Strategy Using Phosphorus Ligand-Coupling

2019 ◽  
Author(s):  
Benjamin T. Boyle ◽  
Michael C. Hilton ◽  
Andrew McNally
Keyword(s):  
Cross Coupling ◽  
Coupling Reactions ◽  
One Pot ◽  
Cross Coupling Reactions ◽  
Alternative Approach ◽  
Metal Catalyzed ◽  
Traditional Approaches ◽  
Coupling Partner ◽  
Coupling Sequence

Distinct approaches to synthesize bis-azine biaryls are in demand as these compounds have multiple applications in the chemical sciences and are challenging targets for metal-catalyzed cross-coupling reactions. Most approaches focus on developing new reagents as the formal nucleophilic coupling partner that can function in metal-catalyzed processes. We present an alternative approach using pyridine and diazine phosphines as nucleophilic partners and chloroazines where the heterobiaryl bond is formed via a tandem S<sub><i>N</i></sub>Ar-phosphorus ligand-coupling sequence. The heteroaryl phosphines are prepared from chloroazines and are bench stable solids. Using this strategy, a range of bis-azine biaryls can be formed from abundant chloroazines that would be challenging using traditional approaches and a one-pot cross-electrophile coupling of two chloroazines is feasible.

Metal-Free Photoredox-Catalyzed C–H/C–H Coupling of Arenes Enabled by Interrupted Pummerer Activation

2019 ◽  
Author(s):  
Miles Aukland ◽  
Mindaugas Šiaučiulis ◽  
Adam West ◽  
Gregory Perry ◽  
David Procter
Keyword(s):  
Natural Product ◽  
Selective Reduction ◽  
Cross Coupling ◽  
One Pot ◽  
Complex Molecules ◽  
Pummerer Reaction ◽  
Metal Free ◽  
Bond Forming ◽  
Coupling Partner ◽  
Bioactive Natural Product

<p>Aryl–aryl cross-coupling constitutes one of the most widely used procedures for the synthesis of high-value materials, ranging from pharmaceuticals to organic electronics and conducting polymers. The assembly of (hetero)biaryl scaffolds generally requires multiple steps; coupling partners must be functionalized before the key bond-forming event is considered. Thus, the development of selective C–H arylation processes in arenes, that side-step the need for prefunctionalized partners, is crucial for streamlining the construction of these key architectures. Here we report an expedient, one-pot assembly of (hetero)biaryl motifs using photocatalysis and two non-prefunctionalized arene partners. The approach is underpinned by the activation of a C–H bond in an arene coupling partner using the interrupted Pummerer reaction. A unique pairing of the organic photoredox catalyst and the intermediate dibenzothiophenium salts enables highly selective reduction in the presence of sensitive functionalities. The utility of the metal-free, one-pot strategy is exemplified by the synthesis of a bioactive natural product and the modification of complex molecules of societal importance.</p>

scholarly journals Nickel-Catalyzed Asymmetric Reductive Cross-Coupling of α-Chloroesters with (Hetero)Aryl Iodides

2021 ◽  
Author(s):  
Travis DeLano ◽  
Sara Dibrell ◽  
Caitlin R. Lacker ◽  
Adam Pancoast ◽  
Kelsey Poremba ◽  
...  
Keyword(s):  
Cross Coupling ◽  
Mild Conditions ◽  
Aryl Iodides ◽  
Reaction Proceeds

An asymmetric reductive cross-coupling of α-chloroesters and (hetero)aryl iodides is reported. This nickel-catalyzed reaction proceeds with a chiral BiOX ligand under mild conditions, affording α-arylesters in good yields and enantioselectivities....

scholarly journals Phosphite-Mediated Reductive Cross-Coupling of Isatins and Nitro­styrenes

Synthesis ◽  
2017 ◽  
Vol 49 (12) ◽  
pp. 2663-2676 ◽  
Author(s):  
Somayeh Motevalli ◽  
Jeffrey Johnson
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Reductive Coupling ◽  
Title Reaction ◽  
Dimethyl Phosphite ◽  
Mild Conditions ◽  
Michael Type Addition

A new reductive coupling reaction between N-alkylisatins, dimethyl phosphite, and nitrostyrenes has been developed. The reaction relies on Pudovik addition, subsequent phosphonate–phosphate rearrangement, and Michael-type addition of a transient carbanion on the indolinone with β-nitrostyrenes. This protocol introduces a convenient and versatile method for the construction of polyfunctionalized tertiary phosphates under mild conditions. Chiral general bases catalyze the title reaction with promising levels of enantioselectivity.

Ni-catalyzed direct iminoalkynylation of unactivated olefins with terminal alkynes: facile access to alkyne-labelled pyrrolines

2021 ◽  
Author(s):  
Xingjie Zhang ◽  
Di Qi ◽  
Chenchen Jiao ◽  
Zhiguo Zhang ◽  
Xiaopan Liu ◽  
...  
Keyword(s):  
Radical Cyclization ◽  
Terminal Alkynes ◽  
Mild Conditions ◽  
Type Coupling ◽  
First Time

The direct iminoalkynylation of unactivated olefins with terminal alkynes is achieved for the first time by nickel-catalyzed cascade iminyl-radical cyclization/Sonogashira-type coupling of γ,δ-unsaturated oxime esters under mild conditions. This transformation...

scholarly journals Heterobiaryl synthesis by contractive C–C coupling via P(V) intermediates

Science ◽  
2018 ◽  
Vol 362 (6416) ◽  
pp. 799-804 ◽  
Author(s):  
Michael C. Hilton ◽  
Xuan Zhang ◽  
Benjamin T. Boyle ◽  
Juan V. Alegre-Requena ◽  
Robert S. Paton ◽  
...  
Keyword(s):  
Cross Coupling ◽  
The Other ◽  
Coupling Reactions ◽  
Mechanistic Studies ◽  
Alternative Approach ◽  
Metal Catalyzed ◽  
Polar Functional Groups ◽  
Pharmacological Function ◽  
Complex Drug ◽  
Acidic Alcohol

Heterobiaryls composed of pyridine and diazine rings are key components of pharmaceuticals and are often central to pharmacological function. We present an alternative approach to metal-catalyzed cross-coupling to make heterobiaryls using contractive phosphorus C–C couplings, also termed phosphorus ligand coupling reactions. The process starts by regioselective phosphorus substitution of the C–H bonds para to nitrogen in two successive heterocycles; ligand coupling is then triggered via acidic alcohol solutions to form the heterobiaryl bond. Mechanistic studies imply that ligand coupling is an asynchronous process involving migration of one heterocycle to the ipso position of the other around a central pentacoordinate P(V) atom. The strategy can be applied to complex drug-like molecules containing multiple reactive sites and polar functional groups, and also enables convergent coupling of drug fragments and late-stage heteroarylation of pharmaceuticals.

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